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Keywords:

  • charge transfer;
  • donor–acceptor systems;
  • nanographene;
  • redox chemistry;
  • tetrathiafulvalene

Abstract

An efficient synthetic approach to a symmetrically functionalized tetrathiafulvalene (TTF) derivative with two diamine moieties, 2-[5,6-diamino-4,7-bis(4-pentylphenoxy)-1,3-benzodithiol-2-ylidene]-4,7-bis(4-pentylphenoxy)-1,3-benzodithiole-5,6-diamine (2), is reported. The subsequent Schiff-base reactions of 2 afford large π-conjugated multiple donor–acceptor (D–A) arrays, for example, the triad 2-[4,9-bis(4-pentylphenoxy)-1,3-dithiolo[4,5-g]quinoxalin-2-ylidene]-4,9-bis(4-pentylphenoxy)-1,3-dithiolo[4,5-g]quinoxaline (8) and the corresponding tetrabenz[bc,ef,hi,uv]ovalene-fused pentad 1, in good yields and high purity. The novel redox-active nanographene 1 is so far the largest known TTF-functionalized polycyclic aromatic hydrocarbon (PAH) with a well-resolved 1H NMR spectrum. The electrochemically highly amphoteric pentad 1 and triad 8 exhibit various electronically excited charge-transfer states in different oxidation states, thus leading to intense optical intramolecular charge-transfer (ICT) absorbances over a wide spectral range. The chemical and electrochemical oxidations of 1 result in an unprecedented TTF⋅+ radical cation dimerization, thereby leading to the formation of [1⋅+]2 at room temperature in solution due to the stabilizing effect, which arises from strong π–π interactions. Moreover, ICT fluorescence is observed with large solvent-dependent Stokes shifts and quantum efficiencies of 0.05 for 1 and 0.035 for 8 in dichloromethane.

Featured Compounds

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  1. 1 - 7
Compound 2
Molecular Weight:1013.445
Molecular Formula:C58H68N4O4S4
InChIKey:GRIGEVASKISWAK-UHFFFAOYSA-N
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Compound 8
Molecular Weight:1057.456
Molecular Formula:C62H64N4O4S4
InChIKey:AADDYOSOFLMGMG-UHFFFAOYSA-N
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Compound 1
Molecular Weight:2767.853
Molecular Formula:C194H188N4O4S4
InChIKey:CQBDLNPIVXQMFI-UHFFFAOYSA-N
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Compound 6
Molecular Weight:1069.511
Molecular Formula:C58H60N4O4S6
InChIKey:BRCBXINICJLTAM-UHFFFAOYSA-N
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Compound 4
Molecular Weight:384.091
Molecular Formula:C7Br2N2OS3
InChIKey:ITOCQGBMUBWZQF-UHFFFAOYSA-N
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Compound 5
Molecular Weight:736.183
Molecular Formula:C14Br4N4S6
InChIKey:BVYBKDAQOJNUPK-UHFFFAOYSA-N
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Compound 3
Molecular Weight:242.364
Molecular Formula:C7H2N2S4
InChIKey:HSNHINFLSMBQFD-UHFFFAOYSA-N
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